DE1301050B - Process for joining textiles with rubber - Google Patents

Description

In the case of certain rubber objects, the aldehyde or acetone or acetaldehyde resin and are true, in use there is a considerable need - another one that forms condensation resins with them To withstand stresses, the rubber containing component is layered onto a textile material or layers is made to stretch relatively little, the dried precipitate reinforced textile materials. So usually 5 a rubber treatment bath can contain, wise hoses, tapes and tires made of rubber with and heating the composite body for vulcanization Textile thread in the form of yarns, cords or rubber consists of the fact that one more weave reinforced. In such articles it is a methylolated or resin-forming component essential that the layers or layers of the acetoxymethylated 1-nitroalkane with 1 to 3 carbon reinforcing agents Material firmly used on the rubber between io atoms of matter.

the textile layers are bound and thus, surprisingly, it was found that effective remain connected when the article turns the second resin-forming compound is subjected to deformations in use, since each measure of the invention is an extremely effective one Separation or relative movement of the rubber and bond between textile material and rubber be textile parts for abrasion between these parts and 15 already when using relatively small amounts of the accordingly leads to breakage. To improve connection occurs, taking during the procedure the adhesion of the textile material to the rubber between no disturbing or harmful side effects The textile layers will usually be stepped down. The bond created between the fabric lay made of rubber on the textile material, e.g. B. a material and the rubber holds strong mecha tire cord fabric, applied by the textiles withstanding ao nical stresses, through a bath of an aqueous rubber dispersion. In practicing the process of FIG

is directed. The bath preferably contains a resin, the invention is the textile material, which is untreated z. B. a fusible, partially condensed Resor bath or treated with a latex resin bath, cin-formaldehyde resin, for example in relation to the rubber layers bound in that from 1 mole of resorcinol to about 0.5 to 0.8 mole form- 25 one in the solid rubber mixture as a second resin aldehyde, or an agent that supplies formaldehyde, forming compound e.g. B. Trimethylolnitromethane, so that during subsequent heating, e.g. B. during 1,1 - dimethylol - 1 - nitroethane, 1,1 - dimethylolder Vulcanization of the rubber between the 1 - nitropropane | Tri - (acetoxymethyl) - nitromethane, Textile layers the meltable resin up to the un- 1,1 - di- (acetoxymethyl) - 1-nitroethane or 1,1-di-, fusible state is cured. 30 (acetoxymethyty-l-nitropropane (hereinafter in general

It is known to connect rubber with common "component A" called), along with the Textiles resorcinol and paraformaldehyde in the other resin-forming compound ("component B") Rubber compound to be used. The Paraform- z. B. m-aminophenol, m-phenylenediamine, resorcinol aldehyde However, it is difficult to convert monoacetate, resorcinol diacetate or 1,5-naphthalenediol into rubber mix and is relatively easily decomposable and volatile, 35 or a fusible condensate of resorcinol and so that the paraformaldehyde concentration with the formaldehyde in the ratio of 1 mole resorcinol Age of the rubber mixture before vulcanization about 0.5 to 0.8 mol of formaldehyde or a condensate decreases. In particular, this method also consists of resorcinol and acetone in a ratio of 1 mol the negative odor of paraformaldehyde is bothersome. Resorcinol to about 0.5 to 2 moles of acetone or a con-farther it is known to connect textiles 40 densates made of resorcinol and acetaldehyde in the ratio To use rubber compounds with rubber, from 1 mole of resorcinol to about 0.5 to 1 mole of acetaldehyde the trimeric methyleneaminoacetonitrile and 1.5 naph- incorporated. Such fusible, partially reacted thalinediol or m-disubstituted benzene derivatives ent- resorcinol-formaldehyde resins, and those in keep. In this process, ver-methyleneaminoacetonitrile evolves from the latex resin baths mentioned above annoying vapors, so that at 45 turns, can be produced in a known manner handling difficulties arise. Furthermore, by making a concentrated aqueous solution Methylenaminoacetonitrile is relatively easy to decompose, resorcinol and formaldehyde with or without catalysis. sator, e.g. B. oxalic acid is heated. The softening

Finally, it is known to use latex resin baths according to the ball and ring method (ASTM-impregnated threads in rubber mixtures would include E28-58T) in such meltable, partially embedding resins, the resorcinol and hexamethylenetetramine reacted resins are generally included about 60 included. In this process for use up to 120 ° C. The resorcinol-acetone condensation compounds are, however, relatively weak products, which are white powders, so that larger amounts can also be used in a known manner must, wherein the additional disadvantage turn 55 by acetone and resorcinol in dilute hydrochloric acid occurs, that the hexamethylenetetramine dermatitis comparable at temperatures of 35 to 50 ⁰ C for several hours ursacht. Finally, the hexamethylenetetramine is long to be implemented. The resorcinol acetaldehyde is also relatively easily decomposable. Condensation products that make sticky reddish oils

The object of the invention is therefore to provide textiles and can be produced in a known manner, Solid rubber using such agents by combining acetaldehyde and resorcinol in dilute oxalic compounds, which are easy to handle and have already converted an acid solution for several hours at 100 ° C are highly effective in relatively small amounts. will. The trimethylolnitromethane and the others

The method according to the invention for connecting analog connections are known; see »Aldehydes of Textiles with rubber in which a solid, vul-nitroparaffin condensation «at Vanderbilt canisable rubber compound comprising a meta-di- 65 et al., Ind. Eng. Chem. 32, 34-38 (1940). substituted benzene, in which each substituent is a

OH-, NH ₂ - or CH ₃ CO-ReSt or 1,5-naphthalene-lands a solid vulcanizable rubber diol or a partially condensed resorcinol molding mixture on the textile material in general

3 4

both sides, ζ. B. As with the usual coating. The invention is illustrated in more detail below with reference to some examples of tire cord fabric with tire carcass material. All parts and percentages are applied. Component A and the information refer to the weight,
component B can be mixed with the usual ingredients for solid rubber material in a Banbury- 5

Mixer are mixed. After building the kau- Example 1
chuk-covered textile material for the final

Object, e.g. B. a tire, the layer A rubber compound A was prepared in body heated to vulcanize the rubber. 100 parts natural rubber, 33 parts carbon black, The ratio of component A to component B is 1.25 parts resorcinol, 10 parts zinc oxide, 2 parts stearin not critical and is generally from 0.4 to acid, 5 parts of tar oil plasticizer, 1.5 parts of a Kon-4 Parts of component A per part of component B. Also the densation product of acetone and diphenylamine, Amount of components A and B together in 0.4 parts N - tert-butyl - 2 - benzothiazylsulfenamide, Mixing with the rubber is not critical. In 1.72 parts of trimethylolnitromethane and 3.5 parts of Schweallgemeinen 0.5 to 8 parts, preferably 1 to 15 parts, have been mixed.

4 parts of component A and component B (in total) each

100 parts of rubber used. If the textile mixture A produced, but with the exception that

material, only 1.05 parts of trimethylolnitromethane were added through a rubber latex resin adhesive bath

has been passed, the amount that has been lowered amounts to.

Impact on the textile material in the range from 1 to ao. A rubber compound C became similar to that of

15%> preferably 2 to 10 ° / ₀ latex solids prepared using Mixture A, but with the exception that

drew on the weight of the textile material. only 0.57 part of trimethylolnitromethane added

Natural chewing materials are used as rubber materials.

Tschuk (Hevea) or synthetic rubber made from Rubber mixtures D,

conjugated diolefins or mixtures thereof, one E and F similar to mixtures A, B and C, respectively.

finally their regenerates, in question. The aqueous put, with the exception, however, that 1.25 parts

Rubber dispersion can, if added to the solution, m-aminophenol instead of resorcinol

treatment «of the textile material before coating with.

The solid rubber mixture is also used, there were also rubber mixtures G, H if they consist of this rubber. The synthe- 30 and I produced similar to the mixtures A, B and C, tables rubber polymers from conjugated di- but with the exception that 1.25 parts of m-phenylene olefins are those from z. B. butadiene (1,3), isoprene, diamine were added instead of resorcinol.
2,3-Dimethylbutadiene- (1,3), and also mixed poly- A rubber mixture J was prepared in a similar way merisates from mixtures thereof and mixed polymers as the mixture A, but with the sowing of mixtures of one or more such 35 would take, that 1.72 parts of resorcinol monoacetate instead of butadiene (1,3) with one or more other co- of resorcinol and 2 parts of trimethylolnitromethane of polymerizable compounds, for example up to 1.72 parts of this compound added to 60 percent by weight of such a mixture became.

one or more monoethylene compounds. Furthermore, a rubber mixture was used in

genes containing an α-methylene group, prepared in a similar manner to mixture A, but

at least one of the unbound valences to one with the exception that 2.20 parts of resorcinol diacetate

electronegative group is bound, d. H. in place of resorcinol and 2 parts of trimethylolnitro

Group that the electrical dissymmetry or the methane in place of 1.72 parts of this compound

significantly increases the polar character of the molecule. were admitted.

Examples of compounds which have a «-Methylene 45 rubber mixtures L and M were in similar-

group and produced with butadiene- (1,3) mixed manner like the mixture A, with the

are polymerizable are aryl olefins, e.g. B. styrene, except that 1.75 parts or 2 parts of 1,1-di-

Vinyltoluene, alpha-methylstyrene, the chlorostyrenes, methylol-1-nitroethane instead of trimethylolnitro-

Vinylnaphthalene, and also the alpha-methylenecarbon methane were added.

acids and their esters, nitriles and amides, e.g. B. 50 rubber compounds N and O were

Acrylic acid, methyl acrylate, methyl methacrylate, acrylic Licher way as the mixture A produced with the

nitrile, methacrylonitrile, methacrylamide, the exception, however, that 1.75 or 2 parts of 1,1-dimethyl-

Vinyl pyridines, e.g. B. 2-vinylpyridine, 2-methyl-5-vinyl-ol-1-nitroprop'an instead of trimethylolnitromethane

pyridine, and methyl vinyl ketone. Examples of such have been added.

synthetic rubber polymers made from conjugate 55 A rubber mixture P was similar Gated diolefins are polybutadiene, polyisoprene, prepared in the same way as mixture A, with the butadiene-styrene copolymers and butadiene, however, 1.25 parts of m-aminophenol would be assumed Acrylonitrile copolymers. The rubber also contains resorcinol and 2 parts 1,1-dimethylol Usual approach and Vulkanisationsstock- 1-nitroethane in place of trimethylolnitromethane allot, z. B. carbon black, treatment and plasticizer oils, 60 were given.

which are added as such or from oil A rubber mixture Q was similar Extended rubber may be present, such as the compound A produced, with the exception Antioxidants, sulfur, zinc oxide and assume, however, that 1.82 parts of 1,5-naphthalenediol Accelerator. The textiles can be any kind of resorcinol and 2 parts 1,1-dimethylol, z. B. from natural cellulose (for example 65 1-nitroethane instead of trimethylolnitromethane. Cotton), regenerated cellulose (for example, were added.

Rayon) and synthetic linear polyamides; Furthermore, a rubber mixture R in

this can be cord or fabric. in a similar manner to mixture A made with

with the exception, however, that 1.25 parts of m-aminophenol instead of resorcinol and 2 parts of 1,1-dimethylol-1-nitropropane were added instead of trimethylolnitromethane.

A rubber compound S was prepared in a similar manner to compound A, but with the Except that 1.82 parts of 1,5-naphthalenediol are present Place of resorcinol and 2 parts of 1,1-dimethylol-1-nitropropane were added instead of trimethylolnitromethane.

Rubber Compound T was prepared in a manner similar to Compound A with the exception of however, that 3.65 parts of tri- (acetoxymethyl) nitromethane instead of trimethylolnitromethane were admitted.

A rubber compound U was prepared in a manner similar to compound A, with the exception however, that 3.24 parts of l, l-di- (acetoxymethyl) -1-nitroethane instead of trimethylolnitromethane were admitted.

A rubber compound V was prepared in a manner similar to compound A, with the exception however, that 3.13 parts of 1,1-di- (acetoxymethyl) -1-nitropropane instead of 1.72 parts of trimethylolnitromethane were admitted.

Control rubber compounds were prepared in a manner similar to compound A, but with the Except that resorcinol and trimethylolnitromethane were omitted.

mixture Artificial silk (gray) Polyamide (gray) N 4.35
4.13
3.95
4.04
4.13
3.76
3.72
2.18
3.04 6.67
7.43
6.67
6.35
6.85
8.03
8.34
8.07
9.53 O 1.0 1.63 P. Q R. S. T U V control (Average)

Tire cord made of rayon and polyamide fibers was measured at 121 ° C. according to the "H" adhesion test (described in India Rubber World, Vol. 114,

Example 2

A rubber mixture A was prepared by adding 68 parts of an oil-extended copolymer from about 77 parts of butadiene and 23 parts of styrene, (containing 18 parts of oil), 50 parts of natural Rubber, 25 parts of fully regenerated tires with about 50% rubber or rubber content, 50 parts of carbon black, 1.25 parts of resorcinol, 1.5 parts of stearic acid, 1 part of an alkylated bisphenol, 3 parts of an extending oil, 10 parts Zinc oxide, 4.0 parts tar oil, 0.85 part N-cyclohexyl-2-benzothiazylsulfenamide, 1.5 parts of diphenylguanidine, 2 parts of trimethylolnitromethane and 3.5 parts of sulfur were mixed.

It became a rubber compound B in a similar manner

The adhesion of the rubber mixtures A to V 30 is produced in the same way as the mixture A, with the and the control mixes of pure (gray) would assume 1.25 parts of m-phenylenediamine

Resorcinol were added in place.

A rubber compound C was prepared in a manner similar to compound A, but with the

S. 213 (1946), "Study of the""Test for Evaluating 35 Exception that 1.25 parts of m-aminophenol were added in place of the Adhesive Properties of Tire Cord in Natural and of resorcinol.
GR-S Rubbers «), furthermore according to the ASTM specification. A rubber mixture D was similar

D-2138-62T. In this test, the method to be tested is prepared like mixture A, but with the Cord which, with the exception of the rubber mixture to be tested, coated 2.0 parts of a condensation product is, in two separate standard rubbers made of equimolar proportions of resorcinol and acetone blocks embedded, and the arrangement is vulcani- site of resorcinol were added.

Rubber Compound E was prepared in a manner similar to Compound A with the exception of however, that 2.1 parts of an industrial, fusible, partially condensed resorcinol-formaldehyde resin (Ratio of 1 mol of resorcinol to about 0.6 to 0.8 mol of formaldehyde) instead of resorcinol were added.

Furthermore, a rubber compound F was prepared in a manner similar to that of compound A, with the exception, however, that 2 parts of 1,1-dimethylol-1-nitroethane instead of trimethylolnitromethane and 2 parts of a condensation product of equimolar Portions of resorcinol and acetone were added instead of resorcinol.

A rubber compound G was prepared in a manner similar to compound A, with the exception however, that 2 parts of 1,1-dimethylol-l-nitroethane instead of trimethylolnitromethane and 2 parts of a condensation product of resorcinol and acetaldehyde in the ratio of 0.6 mol of acetaldehyde per mol of resorcinol were added instead of resorcinol. A rubber compound H was prepared in a manner similar to compound A, but with the Exception that 2 parts of 1,1-dimethylol-l-nitroethane instead of trimethylolnitromethane and 2 parts of a technical, fusible, partially condensed Resorcinol formaldehyde resin (ratio of

sated. The force in kg that is necessary to pull the bonded cord freely from one of the rubber blocks is the "H" adhesion value. The higher the value, the better the adhesion of the rubber coating to the cord. Test pieces of the rubber compositions A to V and of the control samples were cured for 30 minutes at 153 ⁰ C. The results are illustrated in the table below:

121 ° C; "!!" - adhesion (in Artificial silk (gray) kg) mixture 3.95
3.36
1.5
2.59
4.49
3.99
6.4
6.99
4.26
4.59
4.4
3.95
3.58 Polyamide (gray) A. 4.9
2.68
2.22
2.18
3.72
3.45
4.81
4.85
3.04
4.45
4.22
4.85
4.54 B. C. D. E. F. G H I. J K L. M.

mixture Arts
silk
(Gray) polyamide
(Gray) Arts
silk
(treat
delt) polyamide
(treat
delt) A. 4.95
3.76
1.72
2.9
5.27
1.77
5.13
5.72
2.54
6.44
5.31
0.5 3.76
1.41
1.41
3.13
4.63
2.49
2.09
3.31
3.63
5.22
3.81
0.77 7.08
7.12
5.13 7.39 B. C. 7.08
7.66 D. E. F. G H I. 4.9 J K Control ....

1 mole of resorcinol to about 0.6 to 0.8 mole of formaldehyde) vulcanized for 30 minutes. The results are in the were added in place of resorcinol. the table below illustrates:

A rubber compound I was similar

Way as the mixture A produced, with the output 121 ⁰ C; "H" adhesion (in kg)

would take, however, that 2 parts of 1,1-dimethylol-l-nitro-5
propane instead of trimethylolnitromethane and

2 parts of a condensation product from equimolar
Proportions of resorcinol and acetone instead of resorcinol
were added.

Furthermore, a rubber mixture J in ahn- io
Licher way produced like the mixture A, however
with the exception that 2 parts of 1,1-dimethylol-l-nitropropane instead of trimethylolnitromethane and
2 parts of a condensation product from resorcinol
and acetaldehyde in the ratio of 0.6 mole acetone vs.
aldehyde per mole of resorcinol instead of resorcinol
were added.

A rubber compound K was similar
Prepared in the same way as mixture A, with the exception, however, that 2 parts of 1,1-dimethylol-l-nitro-ao
propane instead of trimethylolnitromethane and
2 parts of a technical, fusible, partially condensed resorcinol-formaldehyde resin (ratio
from 1 mole of resorcinol to about 0.6 to 0.8 mole of formaldehyde) were added instead of resorcinol. as B eis ρ ie 1 3

A control rubber compound was also used

made in a similar manner to compound A, with A rubber compound A was thereby produced Except, however, that resorcinol and trimethylol are made, that 72 parts of natural rubber, 28 parts nitromethane have been omitted. cis-1,4-polybutadiene, 25 parts of carbon black, 1.25 parts of resor-

The adhesion of the rubber mixtures A to K 30 a, 10 parts of zinc oxide, 2.5 parts of a condensation mixture and the control mixture on an untreated (gray) product made of acetone and diphenylamine, 0.25 part of tire cord made of rayon and polyamide fibers, N ₅ N '- diphenyl - ρ - phenylenediamine, 5 parts of tar oil, and also the rubber mixtures A, D and E 1.5 parts of stearic acid, 0.7 parts of N-morpholinylbenzoan solution-treated tire cord made of rayon and thiazyl-2-sulfenamide, 2 parts of trimethylolnitromethane made of polyamide fibers, were after the "H" adhesion 35 and 3.5 parts of sulfur were mixed, test measured at 211 ° C. The solution-treated rubber mixture B was similar

Rayon and polyamide cord materials were made in a manner similar to Mixture A, with the exception However, conventional "latex solution treatment baths" would accept 1.25 parts of m-aminophenol passes and dried. The "solution treatment bath", where resorcinol was added, as it was for the rayon cord materials in this 40 A rubber compound C was made in similar and in the example below was used in the same way as mixture A was prepared, but with the consisted of 80 solid parts of a copolymer except that 1.80 parts of 1,5-naphthalenediol sates of 50 parts of butadiene and 50 parts of styrene, instead of resorcinol, were added. 20 solid parts of a latex from a terpolymer. A rubber mixture D was similar

prepared from 70 parts of butadiene, 15 parts of vinyl pyridine and 45 ways as the mixture A, but with the 15 parts of styrene, 8 parts of a technical, part exception that 2 parts of a condensation product wise condensed resorcinol-formaldehyde resin from equimolar proportions of resorcinol and acetone (Ratio of 1 mole resorcinol to about 0.6-0.8 mole site of resorcinol added. Formaldehyde) with a softening point according to A rubber mixture E was similar

Ball and ring method of about HO ⁰ C, 0.5 parts 50 as prepared as mixture A, with the ammonia and 2 parts formaldehyde, but this would mean that 2 parts of a technical, molten solution treatment bath at a 15 to 20% The partially condensed resorcinol formaldehyde concentration was maintained. The "solution treatment resin (ratio of 1 mole of resorcinol to about 0.6 treatment bath", as used for polyamide cord in this and up to 0.8 mol of formaldehyde) in place of resorcinol in the example below, consisted of 55 added.

from 100 solid parts of a latex from a compound further became a control rubber compound

polymer from 70 parts of butadiene, 15 parts of vinyl prepared in a similar manner to mixture A, jepyridine and 15 parts of styrene, 15 parts of a tech- but with the exception that resorcinol and trimethylolnish, partially condensed resorcinol-formaldehyde nitromethane were omitted. hyd resin (ratio of 1 mol of resorcinol to about 60 The adhesion of the rubber mixtures A to E 0.6 to 0.8 mol of formaldehyde) with a softening and the control sample at the untreated (gray) point according to the ball and ring method of about and silk to lösungsbehandeltem tire cord of synthetic-HO "C, 0.9 parts of ammonia and 4.25 parts by molding and made of polyamide was measured at 121 ⁰ C after the aldehyde, wherein the Lösungsbehandlungsbad at a" H "-Adhäsionstest measured. the test pieces of 15 was maintained to 20% concentration. It 65 rubber compositions A to e and the control is were to this sample customary Latexcordtauch- vulcanized 20 minutes at 153 ⁰ C. the mixtures. test pieces of the rubber compositions A results are verbis in the following table K and the control sample were ^{illustrated at 153 °} C:

121 ⁰ C; "H" adhesion (in kg)

mixture Arts
silk
(Gray) polyamide
(Gray) Arts
silk
(treat
delt) polyamide
(treat
delt) A. 3.81
3.4
3.36
2.86
3.54
1.09, 3.86
3.13
3.13
2.77
2.63
1.59 6.26
6.17
6.3
5.13
5.94
4.4 9.21
7.03
8.3
7.94
8.57
7.43 B. C. D. E. control

Tire cord of rayon and polyamide fibers was measured by the "H" -Adhäsionstest at 121 ⁰ C. Test pieces of the rubber compositions A to D and the control sample were cured for 30 minutes at 153 ⁰ C. The results are illustrated in the table below:

Example, 4

A rubber mixture A was prepared by using 100 parts of a copolymer from a larger proportion of butadiene and a smaller proportion of acrylonitrile, 6 parts of zinc oxide, 55 parts of carbon black, ao 1.25 parts of resorcinol, 1 part of stearic acid, 15 parts of plasticizer [liquid copolymer from one larger proportion of butadiene and a smaller proportion of acrylonitrile (see U.S. Patent 2500983)], 0.6 parts Tetramethylthiuram monosulfide, 2 parts of trimethylol as nitromethane and 1.5 parts sulfur were mixed.

Rubber compounds B, C and D were prepared in a manner similar to compound A, with the exception, however, that instead of resorcinol in mixture A in mixture B 2 parts of a technical, fusible, partially condensed resorcinol-formaldehyde resin (ratio of 1 mol of resorcinol to about 0.6 to 0.8 mol of formaldehyde), with mixture C 2 parts of a condensation product of equimolar Proportions of resorcinol and acetone and, in the case of mixture C, 2 parts of a condensation product of resorcinol and acetaldehyde was added in the proportion of 0.6 mol of acetaldehyde per mol of resorcinol.

A control rubber compound was prepared in a manner similar to Compound A with the Except, however, that resorcinol and trimethylolnitromethane were omitted.

The adhesion of rubber compounds A to D and the control sample to untreated (gray)

121 ⁰ C; "H" adhesion (in Artificial silk (gray) kg) mixture
XO 2.27
4.85
1.77
3.18
0.73 Polyamide (gray) A.
B.
C.
1 $ D: .......
control 2.04
6.26
1.77
4.76
0.95

A comparison of the "H" adhesion values for rubber compounds that are produced according to the invention according to the above examples, with the control samples clearly shows the considerable improvement in the adhesion of fiber material to rubber or rubber, as in accordance with the invention is achieved.

Claims (1)

Claim: Process for joining textiles with rubber by applying a solid vulcanizable rubber mixture which contains a meta-disubstituted benzene, in which each substituent is an OH, NH ₂ or CH ₃ CO residue or 1,5-naphthalenediol or a partially condensed resorcinol Formaldehyde or acetone or acetaldehyde resin and a further component that forms condensation resins therewith, on a textile material which can contain the dried precipitate of a rubber latex treatment bath, and heating the composite body to vulcanize the rubber, characterized in that as the further resin-forming component a methylolated or acetoxymethylated 1-nitroalkane with 1 to 3 carbon atoms is used.